本篇論文分成兩部分：
第一部分為合成金屬奈米粒子於高熱穩定性的金屬有機骨架材料UiO-66中，在有機相下找到金奈米粒子能夠不被溶化掉的條件也能夠被包覆於UiO-66當中，其中找到最佳的條件為在DMF中利用ZrOCl2做為鋯源去反應，但在此狀況合成下的產物並非單晶結構包覆金屬奈米粒子。隨後，為了使綠色化學實踐，以及在DMF下所無法解決的課題-控制MOF的晶體成長與金屬面向呈一規則排序，同樣選擇金奈米粒子，並嘗試在水相下也做Metal@MOF，經過一系列實驗後，發現利用CTAB以及CTAC狀態下的金屬奈米粒子易被包覆，雖然只有少許的例子是一顆金奈米粒子包於一顆UiO-66，然而這是一個重要的里程，未來需要更多的實驗探討去找到最佳化的金屬奈米粒子包覆效果以及金屬面向跟MOF晶體成長的控制，達到探究機理與催化方向的先驅。
第二部分利用UiO-66結晶，將其鍵結在官能基化的中孔矽材CAR-10上面，合出孔洞分級材料，利用FT-IR、XRD以及SEM確認材料是否成功合成，再以等溫氮氣吸脫附儀及熱重分析儀研究材料的孔洞大小和性質，並將材料送測醇水分離的效率，並顯示有不錯的分離結果，未來希望可以將此類的孔洞分級材料應用在其他領域上。

This thesis is sorted by two parts as below:
Part I: Single encapsulation of gold nanoparticle into robust Zr-based metal-organic framework：Evolution of the alignments toward a single Au nanoparticle embedded into an individual UiO-66 nanocrystal: The realization of metal NPs for specific catalytic application is an intensively studied field where numerous efforts are investigated in modulating their active site via the incorporation of the other materials. Additionally, as small sized NPs possess high surface energy, agglomeration during catalytic reaction is presented. Therefore, materials incorporated with metal NPs should either prevent the agglomeration or provide the specific mechanism to tune their catalytic nature. In this study, Zr-based metal-organic frameworks, UiO-66, with microposity and milder synthetic condition is here investigated as the incorporating compositions while the gold NPs is selected as the prototype. By controlling the crystallization of UiO-66 nanocrystal under organic solution, a single particle of UiO-66 nanocrystal is able to encapsulate only one gold NP inside, Au@UiO-66. Notably, the metal precursor of UiO-66 in this study is selected as ZrOCl2 rather than ZrCl4 which often lead to the erosion of gold NPs. Furthermore, to tune the alignments of the Au@UiO-66, the organic solution in previous experiment is switch to the water-based system which is able provide the polarity to modulate the surfactant CTAB and CTAC for the further advanced alignments of Au@UiO-66. Consequently, the resulting chemically robust Au@UiO-66 materials is expected to provide more scopes to tune the catalytic capability of metal NPs as well as be the prototype to establish other Metal NPs@MOFs.

Part ll: Synthesis of Hierarchical Micro/Mesoporous Structure: Zr-based Metal-Organic Framework on SBA-15 for Enhanced Pervaporation of Water/Ethanol Mixtures: A new type of hierarchical micro/mesoporous structure (UiO-66@CAR-10) was achieved by heteroepitaxial growth of Zr-metal organic framework, UiO-66, on the functionalized silica mesoporous material, CAR-10. The synthesized hierarchical micro/mesoporous UiO-66@CAR-10 structure was examined by various spectroscopic techniques. In addition, the pervaporation measurements of the liquid water/ethanol mixture show that UiO-66@CAR-10/PVA (poly(vinylalcohol) mixed-matrix membrane exhibits enhanced performance both on the permeability and separation factor. Compared to the previous reports, this study provides a simple approach for synthesizing novel hierarchical porous composites exhibiting both advantages of mesoporous materials and microporous materials, which is expected to be useful for gas adsorption, separation, and catalysis.

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